Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports

ABSTRACT

Catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidide complexes are disclosed. These catalyst compositions can be used to produce olefin polymers having relatively broad molecular weight distributions and low levels of long chain branching.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent applicationSer. No. 14/510,153, filed on Oct. 9, 2014, now U.S. Pat. No. 9,441,063,the disclosure of which is incorporated herein by reference in itsentirety.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.Traditional Ziegler catalyst systems can produce olefin polymers having,for example, good extrusion processibility and polymer melt strength,typically due to their broad molecular weight distribution (MWD). Insome end-use applications, it can be beneficial for the olefin polymeralso to have low levels of long chain branching. Moreover, it can bebeneficial for the catalyst system employed to efficiently incorporatecomonomer, as well as to have a greater sensitivity to hydrogen toenable a broader range of polymer melt index and molecular weight to beproduced. Accordingly, it is to these ends that the present invention isdirected.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

Generally, the present invention is directed to half-metallocenetitanium compounds, catalyst compositions containing thesehalf-metallocene titanium compounds, methods for preparing the catalystcompositions, methods for using the catalyst compositions to polymerizeolefins, the polymer resins produced using such catalyst compositions,and articles produced using these polymer resins.

According to one aspect of the invention, the half-metallocene titaniumcompound can have the structure of formula (II):

According to another aspect of the invention, the half-metallocenetitanium compound can have the structure of formula (III):

In these formulas, each Cp independently can be any cyclopentadienyl,indenyl, or fluorenyl group disclosed herein, and each X independentlycan be any monoanionic ligand disclosed herein. Independently, R¹, R²,R³, R^(A), and R^(B) can be H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein.

Other aspects of the present invention are directed to catalystcompositions containing any half-metallocene titanium compound disclosedherein, any activator-support disclosed herein, and optionally, anyco-catalyst disclosed herein. Such catalyst compositions can be used toproduce, for example, ethylene-based homopolymers and copolymers forvariety of end-use applications.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer.Generally, the catalyst composition employed can comprise any of thehalf-metallocene titanium compounds and any of the activator-supportsand optional co-catalysts disclosed herein. For example, organoaluminumcompounds can be utilized in the catalyst compositions and/orpolymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene homopolymer orcopolymer) consistent with aspects of this invention can becharacterized by the following properties: a ratio of Mw/Mn in a rangefrom about 4 to about 10 (or from about 5 to about 9), a ratio ofHLMI/MI in a range from about 15 to about 75 (or from about 25 to about55), a density in a range from about 0.89 to about 0.97 g/cm³ (or fromabout 0.92 to about 0.94 g/cm³), less than or equal to about 0.008 longchain branches (LCB) per 1000 total carbon atoms (or less than or equalto about 0.003 LCB), and a conventional comonomer distribution (e.g.,the number of short chain branches (SCB) per 1000 total carbon atoms ofthe polymer at Mn is greater than at Mz).

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of polymersproduced using a catalyst system containing a half-metallocene titaniumcompound (Example 4), produced using a standard metallocene-basedcatalyst system (Example C2), and produced using a standard Zieglercatalyst system (Example C3).

FIG. 2 presents a plot of the short chain branch distribution of apolymer produced using the same experimental conditions as Example 2.

FIG. 3 presents a plot of the radius of gyration versus the molecularweight for a linear standard and polymers produced using the sameexperimental conditions as Example 6.

FIG. 4 presents a plot of the amount of long chain branches (LCB) per1,000,000 total carbon atoms as a function of the molecular weight ofpolymers produced using the same experimental conditions as Example 6.

FIG. 5 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 4 and 21-22, produced usingdifferent amounts of diethylzinc (DEZ).

FIG. 6 presents a plot of the molecular weight distributions of thepolymers of Examples 4 and 21-22, produced using different amounts ofdiethylzinc (DEZ).

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) a half-metallocene titanium compound, (ii) an activator-support,and (iii) optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “ahalf-metallocene titanium compound” is meant to encompass one, ormixtures or combinations of more than one, activator-support orhalf-metallocene titanium compound, respectively, unless otherwisespecified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, thehalf-metallocene titanium compound, or the activator-support, aftercombining these components. Therefore, the terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, encompass theinitial starting components of the composition, as well as whateverproduct(s) may result from contacting these initial starting components,and this is inclusive of both heterogeneous and homogenous catalystsystems or compositions. The terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, can be used interchangeablythroughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component. Combiningadditional materials or components can be done by any suitable method.Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can include reaction products, it isnot required for the respective components to react with one another.Similarly, the term “contacting” is used herein to refer to materialswhich can be blended, mixed, slurried, dissolved, reacted, treated, orotherwise contacted in some other manner. Therefore, the term“contacting” encompasses the “reacting” of two or more components, andit also encompasses the “mixing” or “blending” of two or more componentsthat do not react with one another.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the ratio of Mw/Mnof an olefin polymer produced in an aspect of this invention. By adisclosure that the Mw/Mn can be in a range from about 4 to about 10,Applicants intend to recite that the Mw/Mn can be any ratio in the rangeand, for example, can be equal to about 4, about 5, about 6, about 7,about 8, about 9, or about 10. Additionally, the Mw/Mn can be within anyrange from about 4 to about 10 (for example, from about 5 to about 9),and this also includes any combination of ranges between about 4 andabout 10 (for example, the Mw/Mn can be in a range from about 4 to about6, or from about 7 to about 9). Likewise, all other ranges disclosedherein should be interpreted in a manner similar to these examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing the catalyst compositions, methodsfor using the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto half-metallocene titanium phosphinimide complexes andhalf-metallocene titanium iminoimidazolidide complexes, to catalystcompositions employing these half-metallocene titanium complexes, topolymerization processes utilizing such catalyst compositions, and tothe resulting olefin polymers produced from the polymerizationprocesses.

Titanium Phosphinimides and Titanium Iminoimidazolidides

In an aspect of this invention, the half-metallocene titanium compoundscan have the formula:

Within formula (I), Cp, L, and each X are independent elements of thehalf-metallocene titanium compound. Accordingly, the half-metallocenetitanium compound having formula (I) may be described using anycombination of Cp, L, and X disclosed herein.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

Each X in formula (I) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,—OBR^(X) ₂, or —OSO₂R^(X), wherein R^(X) is a C₁ to C₃₆ hydrocarbylgroup. It is contemplated that each X can be either the same or adifferent monoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR^(X) ₂, or OSO₂R^(X),wherein R^(X) is a C₁ to C₁₈ hydrocarbyl group. In another aspect, eachX independently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group,a C₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, aC₁ to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilylgroup, OBR^(X) ₂, or OSO₂R^(X), wherein R^(X) is a C₁ to C₁₂ hydrocarbylgroup. In another aspect, each X independently can be H, BH₄, a halide,a C₁ to C₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ toC₁₀ hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ toC₁₀ hydrocarbylaminylsilyl group, OBR^(X) ₂, or OSO₂R^(X), wherein R^(X)is a C₁ to C₁₀ hydrocarbyl group. In yet another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, aC₁ to C₈ hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ toC₈ hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group,OBR^(X) ₂, or OSO₂R^(X), wherein R^(X) is a C₁ to C₈ hydrocarbyl group.In still another aspect, each X independently can be a halide or a C₁ toC₁₈ hydrocarbyl group. For example, both X's can be Cl.

The hydrocarbyl group which can be an X (one or both) in formula (I) canbe a C₁ to C₃₆ hydrocarbyl group, including, but not limited to, a C₁ toC₃₆ alkyl group, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkylgroup, a C₆ to C₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. Forinstance, each X independently can be a C₁ to C₁₈ alkyl group, a C₂ toC₁₈ alkenyl group, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group,or a C₇ to C₁₈ aralkyl group; alternatively, each X independently can bea C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, each X independently can be a C₁ to C₁₀ alkyl group, a C₂to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a C₇ to C₁₀ aralkyl group; or alternatively, each Xindependently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, aC₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (I) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (I)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (I) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (I) independently can be a cycloalkyl group,including, but not limited to, a cyclobutyl group, a substitutedcyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group,a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group,a substituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. For example, an X in formula (I) can be a cyclopentylgroup, a substituted cyclopentyl group, a cyclohexyl group, or asubstituted cyclohexyl group. Moreover, each X in formula (I)independently can be a cyclobutyl group or a substituted cyclobutylgroup; alternatively, a cyclopentyl group or a substituted cyclopentylgroup; alternatively, a cyclohexyl group or a substituted cyclohexylgroup; alternatively, a cycloheptyl group or a substituted cycloheptylgroup; alternatively, a cyclooctyl group or a substituted cyclooctylgroup; alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. Substituents which can be utilized forthe substituted cycloalkyl group are independently disclosed herein andcan be utilized without limitation to further describe the substitutedcycloalkyl group which can be an X in formula (I).

In some aspects, the aryl group which can be an X in formula (I) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (I).

In an aspect, the substituted phenyl group which can be an X in formula(I) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X in formula (I).

In some aspects, the aralkyl group which can be an X in formula (I) canbe a benzyl group or a substituted benzyl group. In an aspect, thearalkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X in formula (I).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (I) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (I). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, (alkyl, aryl, or aralkyl)-O-(alkyl,aryl, or aralkyl) groups, and —O(CO)-(hydrogen or hydrocarbyl) groups,and these groups can comprise up to about 36 carbon atoms (e.g., C₁ toC₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxy groups).Illustrative and non-limiting examples of hydrocarboxy groups which canbe an X in formula (I) can include, but are not limited to, a methoxygroup, an ethoxy group, an n-propoxy group, an isopropoxy group, ann-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (I) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (I)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (I) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (I) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, a C₇ to C₈ aralkyl group, etc.). As used herein, hydrocarbylsilylis intended to cover (mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl(—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups, with R being ahydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C₃to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, such as, for example, atrialkylsilyl group or a triphenylsilyl group. Illustrative andnon-limiting examples of hydrocarbylsilyl groups which can be an X informula (I) can include, but are not limited to, trimethylsilyl,triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl,tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X include, but are notlimited to, —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be an X cancomprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ toC₁₂, or C₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, eachhydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be anyhydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group,a C₇ to C₈ aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl isintended to cover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂,—N(SiHR₂)₂, and —N(SiR₃)₂ groups, among others, with R being ahydrocarbyl group.

In an aspect, each X independently can be —OBR^(X) ₂ or —OSO₂R^(X),wherein R^(X) is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁to C₁₈ hydrocarbyl group. The hydrocarbyl group in OBR^(X) ₂ and/orOSO₂R^(X) independently can be any hydrocarbyl group disclosed herein,such as, for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenylgroup, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ toC₁₈ aralkyl group; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂alkenyl group, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, ora C₇ to C₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, aC₂ to C₈ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, or a C₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, both X′s can beH; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, BH₄; alternatively, a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁to C₁₈ hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (I), Cp can be a cyclopentadienyl, indenyl, or fluorenylgroup. In one aspect, for instance, Cp can be an unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group, while in another aspect,Cp can be a substituted cyclopentadienyl, indenyl, or fluorenyl group.In yet another aspect, Cp can be an unsubstituted cyclopentadienylgroup; alternatively, an unsubstituted indenyl group; or alternatively,an unsubstituted fluorenyl group. In still another aspect, Cp can be asubstituted cyclopentadienyl group; alternatively, a substituted indenylgroup; or alternatively, a substituted fluorenyl group.

Accordingly, Cp can be a cyclopentadienyl, indenyl, or fluorenyl group,and can have one or more substituents. Further, the substituent(s) canbe at any suitable position(s) on Cp that conforms to the rules ofchemical valence. The substituent (or each substituent independently)can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group. Hence, the substituent (or eachsubstituent independently) can be H; alternatively, a halide;alternatively, a C₁ to C₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈halogenated hydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxygroup; alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively,a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C36 hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp informula (I) can be any halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilyl group describedherein (e.g., as pertaining to X in formula (I)). A substituent on Cpindependently can be, in certain aspects, a C₁ to C₃₆ halogenatedhydrocarbyl group, where the halogenated hydrocarbyl group indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbyl group. The halogenated hydrocarbylgroup often can be a halogenated alkyl group, a halogenated alkenylgroup, a halogenated cycloalkyl group, a halogenated aryl group, or ahalogenated aralkyl group. Representative and non-limiting halogenatedhydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF₃), andthe like.

As a non-limiting example, a substituent (or each substituentindependently) on Cp can be H, Cl, CF₃, a methyl group, an ethyl group,a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a 2,6-diisopropylphenyl group, a tolylgroup (or other substituted aryl group), a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group; alternatively, H; alternatively, Cl;alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a 2,6-diisopropylphenylgroup; alternatively, a tolyl group; alternatively, a benzyl group;alternatively, a naphthyl group; alternatively, a trimethylsilyl group;alternatively, a triisopropylsilyl group; alternatively, atriphenylsilyl group; alternatively, an allyldimethylsilyl group; oralternatively, a 1-methylcyclohexyl group.

In one aspect, for example, a substituent (or each substituentindependently) on Cp can be H or a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₆linear or branched alkyl group (e.g., a tert-butyl group);alternatively, H, Cl, CF₃, a methyl group, an ethyl group, a propylgroup, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, abenzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group, and the like; alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, a decenyl group, a phenyl group, a 2,6-diisopropylphenylgroup, a tolyl group, or a benzyl group; alternatively, a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, or ahexyl group; alternatively, a methyl group; alternatively, an ethylgroup; alternatively, a propyl group; alternatively, a butyl group; oralternatively, a tert-butyl group.

In formula (I), L can be any phosphinimide or iminoimidazolidide liganddisclosed herein. In one aspect, for instance, the half-metallocenetitanium compound can have the structure of formula (II):

In another aspect, the half-metallocene titanium compound can have thestructure of formula (III):

In formulas (II) and (III), each Cp and X independently can be any Cpand X described herein (e.g., as pertaining to Cp and X in formula (I)).R¹, R², R³, R^(A), and R^(B) independently can be H or a halide, C₁ toC₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ toC₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group. The halide,C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group which canbe R¹, R², R³, R^(A), and/or R^(B) can be any halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group described herein(e.g., as pertaining to substituent options for Cp in formula (I)).

In formula (II), R¹, R², and R³ can be either the same or a differentsubstituent group. In one aspect, R¹, R², and R³ independently can be H,a C₁ to C₁₈ hydrocarbyl group, or a C₁ to C₁₈ hydrocarbylsilyl group. Inanother aspect, R¹, R², and R³ independently can be H or a C₁ to C₁₈hydrocarbyl group. In yet another aspect, R¹, R², and R³ independentlycan be a C₁ to C₆ linear or branched alkyl group (e.g., an isopropylgroup, a tert-butyl group) or a C₃ to C₈ alkenyl group (e.g., a terminalalkenyl group). In still another aspect, R¹, R², and R³ independentlycan be H, Cl, CF₃, a methyl group, an ethyl group, a propyl group, abutyl group (e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group,an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a 2,6-diisopropylphenyl group, a tolyl group, a benzylgroup, a naphthyl group, a trimethylsilyl group, a triisopropylsilylgroup, a triphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group, and the like. In some aspects, at least one ofR¹, R², and R³ can be an alkenyl group, such as a C₃ to C₁₂ alkenylgroup, or a C₃ to C₈ terminal alkenyl group.

In formula (III), R^(A) and R^(B) can be either the same or a differentsubstituent group. In one aspect, R^(A) and R^(B) independently can beH, a C₁ to C₁₈ hydrocarbyl group, or a C₁ to C₁₈ hydrocarbylsilyl group.In another aspect, R^(A) and R^(B) independently can be H or a C₁ to C₁₈hydrocarbyl group. In yet another aspect, R^(A) and R^(B) independentlycan be a C₁ to C₆ linear or branched alkyl group (e.g., a methyl group,an isopropyl group, a tert-butyl group). In still another aspect, R^(A)and R^(B) independently can be H, Cl, CF₃, a methyl group, an ethylgroup, a propyl group, a butyl group (e.g., t-Bu), a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a phenyl group, a2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, an allyldimethylsilyl group, or a1-methylcyclohexyl group, and the like. In some aspects, theheterocyclic carbene group can be saturated, while in other aspects, theheterocyclic carbene group can be unsaturated.

Illustrative and non-limiting examples of half-metallocene titaniumcompounds—having the structure of formula (I), formula (II), and/orformula (III)—suitable for use in catalyst systems and polymerizationprocesses encompassed herein can include the following compounds(tBu=tert-butyl; Ph=phenyl; Cy=cyclohexyl; iPr=isopropyl; X=amonoanionic ligand, such as Cl):

and the like.

Methods of making half-metallocene titanium phosphinimide andhalf-metallocene titanium iminoimidazolidide compounds of the presentinvention also are encompassed herein. These half-metallocene complexescan be synthesized by various suitable procedures, such as thosedescribed in Organometallics 2001, 20, 4424, the disclosure of which isincorporated herein by reference in its entirety.

Using analogous synthesis schemes, half-metallocene complexes withsubstituents on the phosphorus atom other than tert-butyl or pentenylcan be derived, and complexes with cyclopentadienyl or indenyl groupswith various hydrocarbyl and other substituents can be derived.Moreover, using analogous synthesis schemes, half-metallocene complexeswith monoanionic ligands other than Cl (e.g., hydrocarbyl,hydrocarbylaminyl, hydrocarbylsilyl, etc.) can be derived.

Second Metallocene Compounds

In certain aspects of this invention, the catalyst system can contain asecond metallocene compound, in addition to the titaniumhalf-metallocene compound. For example, the second metallocene compoundcan comprise a bridged metallocene compound. In one aspect, the secondmetallocene compound can comprise a bridged zirconium or hafnium basedmetallocene compound. In another aspect, the second metallocene compoundcan comprise a bridged zirconium or hafnium based metallocene compoundwith an alkenyl substituent. In yet another aspect, the secondmetallocene compound can comprise a bridged zirconium or hafnium basedmetallocene compound with an alkenyl substituent and a fluorenyl group.In still another aspect, the second metallocene compound can comprise abridged zirconium or hafnium based metallocene compound with acyclopentadienyl group and a fluorenyl group, and with an alkenylsubstituent on the bridging group and/or on the cyclopentadienyl group.

In an aspect, the second metallocene compound can comprise a single atombridged metallocene compound with a fluorenyl group. In another aspect,the second metallocene compound can comprise a single atom bridgedmetallocene compound with a fluorenyl group and either acyclopentadienyl group or an indenyl group. In yet another aspect, thesecond metallocene compound can comprise a single atom bridgedmetallocene compound with a fluorenyl group and a cyclopentadienylgroup. In still another aspect, the second metallocene compound cancomprise a single atom bridged metallocene compound with a fluorenylgroup and an indenyl group.

In these and other aspects, the bridged metallocene compound can containan aryl substituent (e.g., a phenyl group) on the bridging atom.Additionally or alternatively, the bridged metallocene compound cancontain an alkenyl substituent, for example, on the bridging atom,and/or on the fluorenyl group, and/or on the cyclopentadienyl or indenylgroup.

Illustrative and non-limiting examples of bridged metallocene compoundsthat are suitable for use as a second metallocene compound can includethe following compounds (Me=methyl, Ph=phenyl; t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Further examples of bridged metallocene compounds that are suitable foruse as a second metallocene compound can include, but are not limitedto, the following compounds:

and the like, as well as combinations thereof.

The second metallocene compound is not limited solely to the bridgedmetallocene compounds such as described above. Other suitable bridgedmetallocene compounds are disclosed in U.S. Pat. Nos. 7,026,494,7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047, which areincorporated herein by reference in their entirety.

In certain aspects of this invention, the catalyst system can contain asecond metallocene compound, in addition to the titaniumhalf-metallocene compound, and the second metallocene compound cancomprise an unbridged metallocene compound. In one aspect, the secondmetallocene compound can comprise an unbridged zirconium or hafniumbased metallocene compound and/or an unbridged zirconium and/or hafniumbased dinuclear metallocene compound. In another aspect, the secondmetallocene compound can comprise an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group. In anotheraspect, the second metallocene compound can comprise an unbridgedzirconium or hafnium based metallocene compound containing twocyclopentadienyl groups. In yet another aspect, the second metallocenecompound can comprise an unbridged zirconium or hafnium basedmetallocene compound containing two indenyl groups. In still anotheraspect, the second metallocene compound can comprise an unbridgedzirconium or hafnium based metallocene compound containing acyclopentadienyl and an indenyl group.

In an aspect, the second metallocene compound can comprise an unbridgedzirconium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group,while in another aspect, the second metallocene compound can comprise adinuclear unbridged metallocene compound with an alkenyl linking group.

Illustrative and non-limiting examples of unbridged metallocenecompounds that are suitable for use as the second metallocene compoundcan include the following compounds (Ph=phenyl):

and the like, as well as combinations thereof.

The second metallocene compound is not limited solely to unbridgedmetallocene compounds such as described above, or to suitable unbridgedmetallocene compounds disclosed in U.S. Pat. Nos. 7,199,073, 7,226,886,7,312,283, and 7,619,047, which are incorporated herein by reference intheir entirety. For example, the second metallocene compound cancomprise an unbridged dinuclear metallocene compound, such as thosedescribed in U.S. Pat. Nos. 7,919,639 and 8,080,681, the disclosures ofwhich are incorporated herein by reference in their entirety.Illustrative and non-limiting examples of dinuclear metallocenecompounds suitable for use as the second catalyst compound include thefollowing compounds:

and the like, as well as combinations thereof.Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one aspect, the activator-supportcan comprise a solid oxide treated with an electron-withdrawing anion.Alternatively, in another aspect, the activator-support can comprise asolid oxide treated with an electron-withdrawing anion, the solid oxidecontaining a Lewis-acidic metal ion. Non-limiting examples of suitableactivator-supports are disclosed in, for instance, U.S. Pat. Nos.7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886,which are incorporated herein by reference in their entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163.

Accordingly, in one aspect, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxidethereof, or any combination thereof. In another aspect, the solid oxidecan comprise alumina, silica-alumina, silica-coated alumina, aluminumphosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother aspect, the solid oxide can comprise silica, alumina, titania,zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof, or anycombination thereof. In yet another aspect, the solid oxide can comprisesilica-alumina, silica-coated alumina, silica-titania, silica-zirconia,alumina-boria, or any combination thereof. In still another aspect, thesolid oxide can comprise alumina, silica-alumina, silica-coated alumina,or any mixture thereof; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have an silica content from about 5 to about 95% byweight. In one aspect, the silica content of these solid oxides can befrom about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another aspect, such materials can have silica contentsranging from about 15% to about 60%, or from about 25% to about 50%,silica by weight. The solid oxides contemplated herein can have anysuitable surface area, pore volume, and particle size, as would berecognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspect,the electron-withdrawing component can be an electron-withdrawing anionderived from a salt, an acid, or other compound, such as a volatileorganic compound, that serves as a source or precursor for that anion.Examples of electron-withdrawing anions can include, but are not limitedto, sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, tungstate, molybdate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects provided herein. In other aspects, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof. Yet, in otheraspects, the electron-withdrawing anion can comprise fluoride and/orsulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular aspects provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an aspect, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,as well as any mixture or combination thereof. In another aspect, theactivator-support employed in the catalyst systems described herein canbe, or can comprise, a fluorided solid oxide and/or a sulfated solidoxide, non-limiting examples of which can include fluorided alumina,sulfated alumina, fluorided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, fluorided silica-coated alumina, sulfatedsilica-coated alumina, and the like, as well as combinations thereof. Inyet another aspect, the activator-support can comprise fluoridedalumina; alternatively, chlorided alumina; alternatively, sulfatedalumina; alternatively, fluorided silica-alumina; alternatively,sulfated silica-alumina; alternatively, fluorided silica-zirconia;alternatively, chlorided silica-zirconia; alternatively, sulfatedsilica-coated alumina; or alternatively, fluorided silica-coatedalumina. In some aspects, the activator-support can comprise a fluoridedsolid oxide, while in other aspects, the activator-support can comprisea sulfated solid oxide.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,5997,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscontaining a half-metallocene titanium compound (optionally, a secondmetallocene compound) and an activator-support (one or more than one).These catalyst compositions can be utilized to producepolyolefins—homopolymers, copolymers, and the like—for a variety ofend-use applications. Half-metallocene titanium compounds and optionalsecond metallocene compounds are discussed hereinabove. In aspects ofthe present invention, it is contemplated that the catalyst compositioncan contain more than one half-metallocene titanium compound and/or morethan one second metallocene compound. Further, additional catalyticcompounds—other than those specified as a half-metallocene titaniumcompound or a second metallocene compound—can be employed in thecatalyst compositions and/or the polymerization processes, provided thatthe additional catalytic compound does not detract from the advantagesdisclosed herein. Additionally, more than one activator-support also maybe utilized.

Generally, catalyst compositions of the present invention comprise ahalf-metallocene titanium compound having formula (I) (e.g., formula(II) or (III)) and an activator-support (e.g., a solid oxide treatedwith an electron-withdrawing anion). Activator-supports useful in thepresent invention are disclosed herein. Optionally, such catalystcompositions can further comprise one or more than one secondmetallocene compound or compounds, and/or can further comprise one ormore than one co-catalyst compound or compounds (suitable co-catalysts,such as organoaluminum compounds, also are discussed herein). Thus, acatalyst composition of this invention can comprise a half-metallocenetitanium compound, an activator-support, and an organoaluminum compound(and optionally, a second metallocene compound). For instance, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof; or alternatively, afluorided solid oxide and/or a sulfated solid oxide. Additionally, theorganoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof. Accordingly, a catalyst composition consistent with aspects ofthe invention can comprise (or consist essentially of, or consist of) ahalf-metallocene titanium compound; sulfated alumina (or fluoridedsilica-alumina, or fluorided silica-coated alumina); andtriethylaluminum (or triisobutylaluminum). Optionally, dual catalystsystems can contain a half-metallocene titanium compound and a secondmetallocene compound, as described herein.

In one aspect, a catalyst composition of the present invention cancomprise a half-metallocene titanium compound having formula (II) or(III), a fluorided solid oxide, and optionally, a co-catalyst, such asan organoaluminum compound. Yet, in another aspect, a catalystcomposition of the present invention can comprise a half-metallocenetitanium compound having formula (II) or (III), a sulfated solid oxide,and optionally, a co-catalyst, such as an organoaluminum compound.Additionally, a second metallocene compound can be included in thesecatalyst compositions, if desired.

In another aspect of the present invention, a catalyst composition isprovided which comprises a half-metallocene titanium compound, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially of a half-metallocene titanium compound, anactivator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other aspects of this invention, these co-catalysts can beemployed. For example, a catalyst composition comprising ahalf-metallocene titanium compound and an activator-support can furthercomprise an optional co-catalyst. Suitable co-catalysts in this aspectcan include, but are not limited to, aluminoxane compounds, organoboronor organoborate compounds, ionizing ionic compounds, organoaluminumcompounds, organozinc compounds, organomagnesium compounds,organolithium compounds, and the like, or any combination thereof; oralternatively, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, or any combinationthereof. More than one co-catalyst can be present in the catalystcomposition.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator-support (one or more thanone) and only one half-metallocene titanium compound. In these and otheraspects, the catalyst composition can comprise an activator-supportcomprising a solid oxide treated with an electron-withdrawing anion,only one half-metallocene titanium compound, and a co-catalyst (one ormore than one), such as an organoaluminum compound.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence. In one aspect, the catalystcomposition can be produced by a process comprising contacting thehalf-metallocene titanium compound and the activator-support, while inanother aspect, the catalyst composition can be produced by a processcomprising contacting, in any order, the half-metallocene titaniumcompound, the activator-support, and the co-catalyst.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support are employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of half-metallocenetitanium compound to activator-support can be in a range from about 1:1to about 1:1,000,000. If more than one half-metallocene titaniumcompound and/or more than activator-support is/are employed, this ratiois based on the total weights of the respective components. In anotheraspect, this weight ratio can be in a range from about 1:5 to about1:100,000, or from about 1:10 to about 1:10,000. Yet, in another aspect,the weight ratio of the half-metallocene titanium compound to theactivator-support can be in a range from about 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 10 kg of ethylene polymer (homopolymer orcopolymer, as the context requires) per gram of the half-metallocenetitanium compound per hour (abbreviated kg/g/h). In another aspect, thecatalyst activity can be greater than about 25, greater than about 35,or greater than about 40 kg/g/h. In still another aspect, catalystcompositions of this invention can be characterized by having a catalystactivity greater than about 50, greater than about 100, or greater thanabout 150 kg/g/h, and often can range up to 400, up to 500, or up to 750kg/g/h. These activities are measured under slurry polymerizationconditions, with a triisobutylaluminum co-catalyst, using isobutane asthe diluent, at a polymerization temperature of 80° C. and a reactorpressure of about 340 psig. Additionally, in some aspects, theactivator-support can comprise sulfated alumina, fluoridedsilica-alumina, or fluorided silica-coated alumina, although not limitedthereto.

In aspects of this invention where the catalyst composition contains asecond metallocene compound, the weight ratio of the half-metallocenetitanium compound to the second metallocene compound (e.g., a bridgedmetallocene, an unbridged metallocene) in the catalyst composition canbe in a range from about 10:1 to about 1:10, from about 8:1 to about1:8, from about 5:1 to about 1:5, from about 4:1 to about 1:4, fromabout 3:1 to about 1:3; from about 2:1 to about 1:2, from about 1.5:1 toabout 1:1.5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 toabout 1:1.1.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise a half-metallocene titanium compound,an activator-support, and an optional co-catalyst, and an optionalsecond metallocene compound. Suitable half-metallocene titaniumcompounds, second metallocene compounds, activator-supports, andco-catalysts are discussed herein.

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a half-metallocenetitanium compound having formula (II) or (III) and an activator-support.The catalyst composition, optionally, can further comprise one or morethan one organoaluminum compound or compounds (or other suitableco-catalyst), and/or can further comprise one or more than one secondmetallocene compound or compounds. Thus, a process for polymerizingolefins in the presence of a catalyst composition can employ a catalystcomposition comprising a half-metallocene titanium compound, anactivator-support, and an organoaluminum compound. In some aspects, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof; alternatively, afluorided solid oxide and/or a sulfated solid oxide; alternatively, afluorided solid oxide; or alternatively, a sulfated solid oxide. In someaspects, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof. Optionally, polymerization processes consistentwith aspects of this invention can employ a dual catalyst systemcontaining a half-metallocene titanium compound and a second metallocenecompound, as described herein.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising a half-metallocenetitanium compound, an activator-support, and an optional co-catalyst,wherein the co-catalyst can comprise an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganoaluminum compound, an organozinc compound, an organomagnesiumcompound, or an organolithium compound, or any combination thereof.Hence, aspects of this invention are directed to a process forpolymerizing olefins in the presence of a catalyst composition, theprocess comprising contacting a catalyst composition with an olefinmonomer and optionally an olefin comonomer (one or more) underpolymerization conditions to produce an olefin polymer, and the catalystcomposition can comprise a half-metallocene titanium compound, anactivator-support, and an aluminoxane compound; alternatively, ahalf-metallocene titanium compound, an activator-support, and anorganoboron or organoborate compound; alternatively, a half-metallocenetitanium compound, an activator-support, and an ionizing ionic compound;alternatively, a half-metallocene titanium compound, anactivator-support, and an organoaluminum compound; alternatively, ahalf-metallocene titanium compound, an activator-support, and anorganozinc compound; alternatively, a half-metallocene titaniumcompound, an activator-support, and an organomagnesium compound; oralternatively, a half-metallocene titanium compound, anactivator-support, and an organolithium compound. Furthermore, more thanone co-catalyst can be employed, e.g., an organoaluminum compound and analuminoxane compound, an organoaluminum compound and an ionizing ioniccompound, etc.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising only onehalf-metallocene titanium compound, an activator-support, and anorganoaluminum compound.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 65° C. to about 110° C., from about 70° C. to about100° C., from about 70° C. to about 95° C., or from about 75° C. toabout 95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

In a particular aspect, and unexpectedly, a polymerization process cancomprise contacting a catalyst composition with an olefin monomer and,optionally, an olefin comonomer under polymerization conditions toproduce an olefin polymer (e.g., an ethylene homopolymer or copolymer)characterized by a ratio of Mw/Mn in a range from about 4 to about 10(or from about 5 to about 9), a ratio of HLMI/MI in a range from about15 to about 75 (or from about 25 to about 55), a density in a range fromabout 0.89 to about 0.97 g/cm³ (or from about 0.92 to about 0.94 g/cm³),less than or equal to about 0.008 long chain branches (LCB) per 1000total carbon atoms (or less than or equal to about 0.003 LCB), and aconventional comonomer distribution (e.g., the number of short chainbranches (SCB) per 1000 total carbon atoms of the polymer at Mn isgreater than at Mz). The catalyst composition utilized in this processcan comprise a half-metallocene titanium compound, a fluorided solidoxide (e.g., fluorided silica-alumina, fluorided silica-coated alumina,etc.) or a sulfate solid oxide (e.g., sulfated alumina, etc.), and anoptional co-catalyst (e.g., an organoaluminum compound).

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise a half-metallocene titanium compound, anactivator-support, and an optional co-catalyst, and wherein thepolymerization process is conducted in the absence of added hydrogen (nohydrogen is added to the polymerization reactor system). As one ofordinary skill in the art would recognize, hydrogen can be generatedin-situ by transition metal-based catalyst compositions in variousolefin polymerization processes, and the amount generated can varydepending upon the specific catalyst composition and transition metalcompound employed, the type of polymerization process used, thepolymerization reaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises a half-metallocene titanium compound, anactivator-support, and an optional co-catalyst, and wherein thepolymerization process is conducted in the presence of added hydrogen(hydrogen is added to the polymerization reactor system). For example,the ratio of hydrogen to the olefin monomer in the polymerizationprocess can be controlled, often by the feed ratio of hydrogen to theolefin monomer entering the reactor. The added hydrogen to olefinmonomer ratio in the process can be controlled at a weight ratio whichfalls within a range from about 25 ppm to about 1500 ppm, from about 50to about 1000 ppm, or from about 100 ppm to about 750 ppm.

Unexpectedly, the catalyst compositions and polymerization processes ofthe present invention can be much more sensitive to hydrogen thancomparable catalyst systems and processes employing Ziegler catalysts.In one aspect, for example, an increase in the melt index of the olefinpolymer with the addition of 150 ppmw hydrogen (from 0 to 150 ppm byweight of hydrogen based on the olefin monomer, using the catalystcompositions and polymerization processes described herein) can begreater than the increase in the melt index of an olefin polymerobtained using a Ziegler catalyst system, under the same polymerizationconditions. For instance, the melt index of the olefin polymer (e.g., anethylene/1-hexene copolymer) produced by the process can have anincrease in melt index of at least about 1 g/10 min, based on anincrease in hydrogen:monomer weight ratio (e.g., a hydrogen:ethyleneweight ratio) from 0 to 150 ppmw. In some aspects, this increase inhydrogen can result in an increase of melt index of at least about 1.2g/10 min, of at least about 1.5 g/10 min, or of at least about 2 g/10min, and in some instances, up to about 3 g/10 min, or up to about 5g/10 min.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

In a particular aspect, and unexpectedly, the Mw/Mn ratio of the olefinpolymer produced by the process can decrease as the amount of anorganozinc compound (e.g., diethylzinc) added to the polymerizationreactor system increases. For instance, the Mw/Mn ratio of the polymerproduced by the process in the absence of the organozinc compound can begreater than the Mw/Mn of a polymer produced by the process in thepresence of the organozinc compound, under the same polymerizationconditions. Additionally or alternatively, the z-average molecularweight (Mz) of the olefin polymer produced by the process can decreaseas the amount of an organozinc compound (e.g., diethylzinc) added to thepolymerization reactor system increases. For instance, the Mz of thepolymer produced by the process in the absence of the organozinccompound can be greater than the Mz of a polymer produced by the processin the presence of the organozinc compound, under the samepolymerization conditions. The same polymerization conditions means thatall components used to prepare the catalyst systems are held constant(e.g., same amount/type of half-metallocene compound, same amount/typeof co-catalyst, same amount/type of activator, such as fluoridedsilica-coated alumina, etc.) and all polymerization conditions are heldconstant (e.g., same polymerization temperature, same pressure, etc.).Hence, the only difference is the amount of the organozinc compoundpresent during the polymerization.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymers (e.g.,ethylene/α-olefin copolymers, ethylene homopolymers, etc.) produced byany of the polymerization processes disclosed herein. Articles ofmanufacture can be formed from, and/or can comprise, the polymersproduced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene homopolymer, a propylenehomopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/l-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

The densities of ethylene-based polymers (e.g., ethylene homopolymers,ethylene copolymers) produced using the catalyst systems and processesdisclosed herein often are greater than or equal to about 0.89 g/cm³,for example, greater than or equal to about 0.91 g/cm³, or greater thanor equal to about 0.92 g/cm³. Yet, in particular aspects, the densitycan be in a range from about 0.89 to about 0.97, such as, for example,from about 0.91 to about 0.97, from about 0.91 to about 0.965, fromabout 0.91 to about 0.94, from about 0.92 to about 0.94, or from about0.925 to about 0.945 g/cm³. Unexpectedly, ethylene/α-olefin copolymers(e.g., ethylene/1-hexene copolymers) produced using the catalyst systemsand polymerization processes described herein can have improvedcomonomer incorporation, for example, having a decrease in density of atleast about 0.008 g/cm³, of at least about 0.01 g/cm³, of at least about0.015 g/cm³, or of at least about 0.02 g/cm³, and in some instances, upto about 0.025 g/cm³, or up to about 0.035 g/cm³, based on an increasein comonomer:monomer molar ratio (e.g., a 1-hexene:ethylene molar ratio)from 0 (no comonomer) to a comonomer:monomer molar ratio (e.g., a1-hexene:ethylene molar ratio) of 0.0176:1.

In some aspects, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 4 to about 10,from about 4 to about 9, from about 5 to about 10, from about 4.5 toabout 9.5, from about 4.5 to about 9, or from about 5 to about 9, andthe like.

In an aspect, the polymers described herein can have a ratio of HLMI/MIin a range from about 10 to about 80, such as, for instance, from about15 to about 75, from about 20 to about 70, from about 20 to about 65,from about 20 to about 60, or from about 25 to about 55, and the like.

Generally, polymers produced in aspects of the present invention areessentially linear or have very low levels of long chain branching, withtypically less than about 0.01 long chain branches (LCB) per 1000 totalcarbon atoms, and similar in LCB content to polymers shown, for example,in U.S. Pat. Nos. 7,517,939, 8,114,946, and 8,383,754, which areincorporated herein by reference in their entirety. In other aspects,the number of LCB per 1000 total carbon atoms can be less than or equalto about 0.008, less than or equal to about 0.007, less than or equal toabout 0.005, or less than or equal to about 0.003 LCB per 1000 totalcarbon atoms.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described hereinabove can, in someaspects, have a conventional comonomer distribution; generally, thehigher molecular weight components of the polymer have less comonomerincorporation than the lower molecular weight components. Typically,there is decreasing comonomer incorporation with increasing molecularweight. In one aspect, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer can be greater at Mn than at Mw. Inanother aspect, the number of SCB per 1000 total carbon atoms of thepolymer can be greater at Mn than at Mz. In yet another aspect, thenumber of SCB per 1000 total carbon atoms of the polymer can be greaterat Mw than at Mz. In still another aspect, the number of SCB per 1000total carbon atoms of the polymer at a molecular weight of 10⁶ can beless than at a molecular weight of 10⁵.

Olefin polymers, whether homopolymers, copolymers, and so forth, can beformed into various articles of manufacture. Articles which can comprisepolymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a container forchemicals, a drum, a fiber or fabric, a food packaging film orcontainer, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, an outdoor storage product, outdoor play equipment, a pipe, asheet or tape, a toy, or a traffic barrier, and the like. Variousprocesses can be employed to form these articles. Non-limiting examplesof these processes include injection molding, blow molding, rotationalmolding, film extrusion, sheet extrusion, profile extrusion,thermoforming, and the like. Additionally, additives and modifiers areoften added to these polymers in order to provide beneficial polymerprocessing or end-use product attributes. Such processes and materialsare described in Modern Plastics Encyclopedia, Mid-November 1995 Issue,Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials,Properties, TAPPI Press, 1992; the disclosures of which are incorporatedherein by reference in their entirety. In some aspects of thisinvention, an article of manufacture can comprise any of ethylenepolymers described herein, and the article of manufacture can be a filmproduct or a molded product.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise a half-metallocene titanium compound,an activator-support comprising a solid oxide treated with anelectron-withdrawing anion, and an optional co-catalyst (e.g., anorganoaluminum compound); and (ii) forming an article of manufacturecomprising the olefin polymer. The forming step can comprise blending,melt processing, extruding, molding, or thermoforming, and the like,including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Polymer density was determined in grams per cubiccentimeter (g/cm³) on a compression molded sample, cooled at about 15°C. per hour, and conditioned for about 40 hours at room temperature inaccordance with ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, MA) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 400 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the broad standard. The integral table of the broadstandard was pre-determined in a separate experiment with SEC-MALS. Mnis the number-average molecular weight, Mw is the weight-averagemolecular weight, and Mz is the z-average molecular weight.

SEC-MALS combines the methods of size exclusion chromatography (SEC)with multi-angle light scattering (MALS) detection. A DAWN EOS 18-anglelight scattering photometer (Wyatt Technology, Santa Barbara, Calif.)was attached to a PL-210 SEC system (Polymer Labs, now Agilent) or aWaters 150 CV Plus system (Milford, Mass.) through a hot transfer line,thermally controlled at the same temperature as the SEC columns and itsdifferential refractive index (DRI) detector (145° C.). At a flow ratesetting of 0.7 mL/min, the mobile phase, 1,2,4-trichlorobenzene (TCB),was eluted through three, 7.5 mm×300 mm, 20 μm Mixed A-LS columns(Polymer Labs, now Agilent). Polyethylene (PE) solutions withconcentrations of ˜1.2 mg/mL, depending on samples, were prepared at150° C. for 4 hr before being transferred to the SEC injection vialssitting in a carousel heated at 145° C. For polymers of higher molecularweight, longer heating times were necessary in order to obtain truehomogeneous solutions. In addition to acquiring a concentrationchromatogram, seventeen light-scattering chromatograms at differentangles were also acquired for each injection using Wyatt's Astra®software. At each chromatographic slice, both the absolute molecularweight (M) and root mean square (RMS) radius, also known as radius ofgyration (Rg) were obtained from a Debye plot's intercept and slope,respectively. Methods for this process are detailed in Wyatt, P. J.,Anal. Chim. Acta, 272, 1 (1993), which is incorporated herein byreference in its entirety.

The Zimm-Stockmayer approach was used to determine the amount of LCB inFIG. 3. Since SEC-MALS measures M and Rg at each slice of a chromatogramsimultaneously, the branching indices, g_(M), as a function of M couldbe determined at each slice directly by determining the ratio of themean square Rg of branched molecules to that of linear ones, at the sameM, as shown in following equation (subscripts br and lin representbranched and linear polymers, respectively).

$g_{M} = {\frac{\left\langle R_{g} \right\rangle_{br}^{2}}{\left\langle R_{g} \right\rangle_{lin}^{2}}.}$

At a given g_(M), the weight-averaged number of LCB per molecule(B_(3w)) was computed using Zimm-Stockmayer's equation, shown in theequation below, where the branches were assumed to be trifunctional, orY-shaped.

$g_{M} = {\frac{6}{B_{3w}}{\left\{ {{\frac{1}{2}\left( \frac{2 + B_{3w}}{B_{3w}} \right)^{1/2}{\ln\left\lbrack \frac{\left( {2 + B_{3w}} \right)^{1/2} + \left( B_{3w} \right)^{1/2}}{\left( {2 + B_{3w}} \right)^{1/2} - \left( B_{3w} \right)^{1/2}} \right\rbrack}} - 1} \right\}.}}$

LCB frequency (LCB_(Mi)), the number of LCB per 1000 C, of the i^(th)slice was then computed straightforwardly using the following equation(M_(i) is the MW of the i^(th) slice):LCB _(Mi)=1 000*14*B _(3w) /M _(i).

The LCB distribution (LCBD) across the molecular weight distribution(MWD) was thus established for a full polymer.

Short chain branch (SCB) content and short chain branching distribution(SCBD) across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, MA) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IR5 detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter—a. The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$wherein: |η*(ω)|=magnitude of complex shear viscosity;

-   -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

The long chain branches (LCB) per 1,000,000 total carbon atoms of FIG. 4were calculated using the method of Janzen and Colby (J. Mol. Struct.,485/486, 569-584 (1999)), from values of zero shear viscosity, η_(o)(determined from the Carreau-Yasuda model), and measured values of Mwobtained using a Dawn EOS multiangle light scattering detector (Wyatt).See also U.S. Pat. No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y.Yu, D. C. Rohlfing, G. R Hawley, and P. J. DesLauriers, PolymerPreprint, 44, 50, (2003). These references are incorporated herein byreference in their entirety.

Fluorided silica-coated alumina activator-supports were prepared asfollows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g, apore volume of about 1.3 mL/g, and an average particle size of about 100microns. The alumina was first calcined in dry air at about 600° C. forapproximately 6 hours, cooled to ambient temperature, and then contactedwith tetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂.After drying, the silica-coated alumina was calcined at 600° C. for 3hours. Fluorided silica-coated alumina (7 wt. % F) was prepared byimpregnating the calcined silica-coated alumina with an ammoniumbifluoride solution in methanol, drying, and then calcining for 3 hoursat 600° C. in dry air. Afterward, the fluorided silica-coated alumina(FSCA) was collected and stored under dry nitrogen, and was used withoutexposure to the atmosphere.

Examples 1-22 were produced using the following polymerization procedure(Table I and Table II summarizes certain information relating to thepolymerization experiments of Examples 1-22). The polymerization runswere conducted in a 2.2-L stainless steel reactor, and isobutane (1.2 L)was used in all runs. Solutions of the half-metallocene compounds andthe metallocene compounds were prepared at about 1 mg/mL in toluene. Theactivator-support (fluorided silica-coated alumina, FSCA),triisobutylaluminum (TIBA), and the half-metallocene solution and/ormetallocene solution were added in that order through a charge portwhile slowly venting isobutane vapor. The charge port was closed andisobutane was added. The contents of the reactor were stirred and heatedto the desired run temperature of 80° C., and ethylene was thenintroduced into the reactor with 1-hexene (grams) and hydrogen (based onppm by weight of the ethylene) as indicated in Table I and Table II.Ethylene and hydrogen were fed on demand at the specified weight ratioto maintain the target pressure of 340 psig pressure for the specifiedlength of the polymerization run. The reactor was maintained at thedesired run temperature throughout the run by an automatedheating-cooling system. The following half-metallocene titaniumcompounds and metallocene compounds were used in Examples 1-22(tBu=tert-butyl; Me=methyl; Ph=phenyl):

Examples 1-22

As shown in Table I, the catalyst compositions used in Examples 1-14employed a half-metallocene titanium compound, and the polymerizationprocesses utilized various amounts of hydrogen and 1-hexene comonomer.Catalyst activities were relatively high, ranging from about 50 to about550 kg of polymer produced per gram of the half-metallocene titanium perhour. For the polymers of Examples 1-8 in which analytical testing wasperformed, as shown in Table III, the ratios of HLMI/MI ranged fromabout 27 to about 53, and the ratios of Mw/Mn ranged from about 4.8 toabout 9.1. FIG. 1 illustrates the molecular weight distributions (amountof polymer versus the logarithm of molecular weight) for the polymers ofExample 4, Example C2, and Example C3. Unexpectedly, the polymerproduced using the half-metallocene titanium compound had a broadmolecular weight distribution, more similar to a traditional Zieglercatalyst than a traditional metallocene catalyst. Despite the relativelybroad molecular weight distribution, the half-metallocene titaniumcatalyst was surprisingly sensitive to the addition of hydrogen (seee.g., Examples 1 and 4 versus Examples 2 and 5), more similar to atraditional metallocene catalyst than a traditional Ziegler catalyst.Additionally, catalyst systems utilizing the half-metallocene titaniumcompound were efficient incorporators of comonomer, as evidenced by thesharp decrease in density as the addition of 1-hexene comonomer wasincreased (see Table I and Table III).

FIG. 2 illustrates the broad MWD characteristics of a polymer producedusing the same experimental conditions as Example 2, as well as,unexpectedly, the generally decreasing number of SCB's as molecularweight increases. FIG. 3 illustrates the low levels of LCB of thepolymers produced using the half-metallocene titanium compound. Theradius of gyration versus the logarithm of the molecular weight for alinear standard and polymers produced using the same experimentalconditions as Example 6, with data from SEC-MALS, is provided in FIG. 3.These polymers were substantially linear with minimal amounts of LCB,e.g., less than about 0.01 LCB, or less than about 0.008 LCB, etc., per1000 total carbon atoms in the 200,000 to 5,000,000 g/mol molecularweight range, or in the 500,000 to 2,000,000 g/mol molecular weightrange, of the polymer. The very low levels of long chain branches (LCB),i.e., less than 5 per 1,000,000 total carbon atoms (or less than 2 per1,000,000 total carbon atoms) also is illustrated in FIG. 4, which showsthe very low amount of LCB of polymers produced using the sameexperimental conditions as Example 6 as a function of the polymermolecular weight.

As shown in Table II and Table III, the dual catalyst compositions usedin Examples 15-20 employed a half-metallocene titanium compound and abridged or unbridged metallocene compound, and the polymerizationprocesses utilized various amounts of hydrogen and 1-hexene comonomer.Unlike Ziegler catalysts in combination with traditional metallocenes,Examples 15-20 demonstrated unexpectedly high catalyst productivity, andproduced polymers having a wide range of melt flow, density, andmolecular weight characteristics.

Examples 21-22 were conducted by adding diethylzinc (DEZ) along withTIBA to the initial reactor charge. Unexpectedly, as shown by Table III,the dynamic rheology properties at 190° C. in FIG. 5, and the molecularweight distributions in FIG. 6, the addition of DEZ reduced the Mz andthe ratio of Mw/Mn of the polymer.

Comparative Examples C1-C4 are shown in Table II and respective polymersproperties for C2-C4 are shown Table III. Cl used a catalyst compositioncontaining a half-metallocene titanium compound and MAO in toluene; thiscatalyst system resulted in reactor inoperability due to reactorfouling. C2 employed a representative bridged metallocene based catalystsystem, and resulted in a narrow molecular weight distribution polymer(Mw/Mn of 2.2). C3 was representative Ziegler catalyst system withtriethylaluminum, containing di-n-butyl magnesium and TiCl₄ (Mg:Ti>2:1),and C4 was a representative Ziegler catalyst system withtriethylaluminum, containing a prepolymerized titanium/magnesiumcatalyst.

TABLE I Examples 1-14. 1-hexene H₂ Time Polymer Activity ExampleCatalyst Composition (g) (ppm) (min) (g) (kg/g/hr) 1 2 mg TP1/109 mgFSCA/0.5 mmol TIBA 0 150 17 162 286 2 2 mg TP1/116 mg FSCA/0.5 mmol TIBA0 0 20 297 456 3 2 mg TP1/112 mg FSCA/0.5 mmol TIBA 10 150 20 139 209 42 mg TP1/100 mg FSCA/0.5 mmol TIBA 20 150 20 144 216 5 1 mg TP1/61 mgFSCA/0.25 mmol TIBA 20 0 22 202 551 6 2 mg TP1/99 mg FSCA/0.5 mmol TIBA30 150 17 156 275 7 2 mg TP1/91 mg FSCA/0.5 mmol TIBA 20 150 4 34 255 82 mg TP1/90 mg FSCA/0.5 mmol TIBA 20 150 5 35 210 9 2 mg TP2/103 mgFSCA/0.5 mmol TIBA 0 150 30 188 188 10 1.5 mg TC1/157 mg FSCA/0.5 mmolTIBA 20 0 20 163 326 11 3 mg TP3/38 mg FSCA/0.5 mmol TIBA 0 0 25 106 8512 3 mg TP3/37 mg FSCA/0.5 mmol TIBA 20 0 30 87 58 13 3 mg TP4/37 mgFSCA/0.5 mmol TIBA 0 0 24 107 89 14 3 mg TP4/37 mg FSCA/0.5 mmol TIBA 200 15 125 167

TABLE II Examples 15-22 and Comparative Examples C1-C4. 1-hexene H₂ TimePolymer Activity Example Catalyst Composition (g) (ppm) (min) (g)(kg/g/hr) 15 0.5 mg TP1/1 mg MET1/ 0 150 20 166 332 97 mg FSCA/0.5 mmolTIBA 16 0.5 mg TP1/1 mg MET1/ 20 150 18 172 382 97 mg FSCA/0.5 mmol TIBA17 0.5 mg TP1/1 mg MET2/ 0 400 20 164 328 91 mg FSCA/0.5 mmol TIBA 180.5 mg TP1/1 mg MET2/ 20 400 22 184 335 93 mg FSCA/0.5 mmol TIBA 19 0.5mg TP1/1 mg MET3/ 0 150 22 103 187 93 mg FSCA/0.5 mmol TIBA 20 0.5 mgTP1/1 mg MET3/ 20 150 15  76 203 101 mg FSCA/0.5 mmol TIBA 21 1.5 mgTP1/79 mg FSCA/ 20 150 20 163 326 0.5 mmol TIBA/0.5 mmol DEZ 22 1.5 mgTP1/81 mg FSCA/ 20 150 27 113 167 0.5 mmol TIBA/3.0 mmol DEZ C1 0.25 mgTP1/1 mL 10% MAO in toluene 20  0 21 Fouled Fouled C2 3 mg MET2/44 mgFSCA/0.5 mmol TIBA 20  0 45 126  56 C3 6 mg Ziegler1/0.5 mmol TEA 80 25^(a) 28 124  44 C4 2 mg Ziegler2/0.5 mmol TEA 20  40^(a) 10 174 522^(a)Hydrogen addition listed for C3 and C4 is the ΔP from a 300 mLstorage vessel (psig).

TABLE III Examples 1-8, 15-22, and C2-C4 - Polymer Characterization MIHLMI Density Mn/1000 Mw/1000 Mz/1000 Example (g/10 min) (g/10 min)HLMI/MI (g/cc) (g/mol) (g/mol) (g/mol) Mw/Mn 1 0.04 2.1 52.5 0.9552 45.7316.7 888 6.9 2 0 0 — — — — — — 3 2.0 63.4 31.7 0.9472 29.0 155.8 7025.4 4 1.8 66.7 37.1 0.9393 32.2 154.3 502 4.8 5 0 0 — — — — — — 6 1.556.1 37.4 0.9325 28.1 163.5 509 5.8 7 0.7 33.4 47.7 0.9278 15.7 143.0398 9.1 8 3.3 91.2 27.6 0.9245 20.5 115.4 784 5.6 15 2.4 79.0 32.90.9638 21.8 102.9 319 4.7 16 4.9 157.3 32.1 0.9452 19.0 96.4 420 5.1 171.7 146.0 85.9 0.9592 5.0 115.4 376 23.1 18 3.2 193.8 60.6 0.9321 6.795.1 252 14.2 19 0.6 22.4 37.3 0.9623 25.2 222.6 1757 8.8 20 1.2 69.157.6 0.9384 18.4 184.6 1345 10.0 21 3.5 96.6 27.6 0.9411 14.8 101.4 2816.8 22 8.5 184.0 21.6 0.9457 18.8 73.4 163 3.9 C2 0.07 1.6 22.9 0.9207122.9 269.7 505 2.2 C3 2 77.0 40.5 0.9343 12.3 118.7 460 9.7 C4 0.1 2.135.0 0.9403 72.9 285.6 814 3.9

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1

A catalyst composition comprising any half-metallocene titanium compounddisclosed herein, any activator-support disclosed herein, andoptionally, any co-catalyst disclosed herein, wherein thehalf-metallocene titanium compound has the formula:

wherein:

Cp is any cyclopentadienyl, indenyl, or fluorenyl group disclosedherein;

each X independently is any monoanionic ligand disclosed herein; and

L is any phosphinimide or iminoimidazolidide ligand disclosed herein.

Embodiment 2

The composition defined in embodiment 1, wherein the activator-supportcomprises any solid oxide disclosed herein treated with anyelectron-withdrawing anion disclosed herein.

Embodiment 3

The composition defined in embodiment 1, wherein the activator-supportcomprises fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or any combination thereof.

Embodiment 4

The composition defined in embodiment 1, wherein the activator-supportcomprises a fluorided solid oxide, e.g., fluorided alumina, fluoridedsilica-alumina, fluorided silica-coated alumina, etc., or anycombination thereof.

Embodiment 5

The composition defined in embodiment 1, wherein the activator-supportcomprises a sulfated solid oxide, e.g., sulfated alumina, sulfatedsilica-alumina, sulfated silica-coated alumina, etc., or any combinationthereof.

Embodiment 6

The composition defined in any one of embodiments 1-5, wherein theactivator-support further comprises any metal or metal ion disclosedherein, e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium,tin, tungsten, molybdenum, zirconium, etc., or any combination thereof.

Embodiment 7

The composition defined in any one of embodiments 1-6, wherein thecatalyst composition comprises a co-catalyst, e.g., any co-catalystdisclosed herein.

Embodiment 8

The composition defined in any one of embodiments 1-7, wherein theco-catalyst comprises any organoaluminum compound disclosed herein.

Embodiment 9

The composition defined in embodiment 8, wherein the organoaluminumcompound comprises trimethylaluminum, triethylaluminum,triisobutylaluminum, or a combination thereof.

Embodiment 10

The composition defined in any one of embodiments 1-9, wherein thecatalyst composition is substantially free of aluminoxane compounds,organoboron or organoborate compounds, ionizing ionic compounds, orcombinations thereof.

Embodiment 11

The composition defined in any one of embodiments 1-10, wherein thecatalyst composition is produced by a process comprising contacting, inany order, the titanium compound having formula (I), theactivator-support, and the co-catalyst (if used).

Embodiment 12

The composition defined in any one of embodiments 1-11, wherein thehalf-metallocene titanium compound having formula (I) has the structureof formula (II):

wherein:

Cp is any cyclopentadienyl, indenyl, or fluorenyl group disclosedherein;

each X independently is any monoanionic ligand disclosed herein; and

R¹, R², and R³ independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein.

Embodiment 13

The composition defined in embodiment 12, wherein R¹, R², and R³independently are H or a C₁ to C₁₈ hydrocarbyl group.

Embodiment 14

The composition defined in embodiment 12, wherein at least one of R¹,R², and R³ is a C₃ to C₁₂ alkenyl group.

Embodiment 15

The composition defined in embodiment 12, wherein R¹, R², and R³independently are H, Cl, CF₃, a methyl group, an ethyl group, a propylgroup, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, abenzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group.

Embodiment 16

The composition defined in any one of embodiments 1-11, wherein thehalf-metallocene titanium compound having formula (I) has the structureof formula (III):

wherein:

Cp is any cyclopentadienyl, indenyl, or fluorenyl group disclosedherein;

each X independently is any monoanionic ligand disclosed herein; and

R^(A) and R^(B) independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein.

Embodiment 17

The composition defined in embodiment 16, wherein R^(A) and R^(B)independently are H or a C₁ to C₁₈ hydrocarbyl group.

Embodiment 18

The composition defined in embodiment 16, wherein R^(A) and R^(B)independently are H, Cl, CF₃, a methyl group, an ethyl group, a propylgroup, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, abenzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group.

Embodiment 19

The composition defined in any one of embodiments 16-18, wherein theheterocyclic carbene group is unsaturated.

Embodiment 20

The composition defined in any one of embodiments 1-19, wherein each Xindependently is H, BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁to C₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ toC₃₆ hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,OBR^(X) ₂, or OSO₂R^(X), wherein R^(X) is a C₁ to C₃₆ hydrocarbyl group.

Embodiment 21

The composition defined in any one of embodiments 1-20, wherein each Xindependently is any halide (e.g., Cl) or C₁ to C₁₈ hydrocarbyl group(e.g., benzyl) disclosed herein.

Embodiment 22

The composition defined in any one of embodiments 1-21, wherein each Xindependently is Cl, methyl, phenyl, or benzyl.

Embodiment 23

The composition defined in any one of embodiments 1-22, wherein Cp is anunsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

Embodiment 24

The composition defined in any one of embodiments 1-23, wherein Cp is anunsubstituted indenyl group.

Embodiment 25

The composition defined in any one of embodiments 1-22, wherein Cp is asubstituted cyclopentadienyl, indenyl, or fluorenyl group.

Embodiment 26

The composition defined in embodiment 25, wherein each (one or more)substituent on the substituted cyclopentadienyl, indenyl, or fluorenylgroup independently is H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, ora C₁ to C₃₆ hydrocarbylsilyl group.

Embodiment 27

The composition defined in embodiment 25, wherein each (one or more)substituent on the substituted cyclopentadienyl, indenyl, or fluorenylgroup independently is H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a 2,6-diisopropylphenyl group, a tolyl group, abenzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group.

Embodiment 28

The composition defined in any one of embodiments 1-27, wherein acatalyst activity of the catalyst composition is in any range disclosedherein, e.g., from about 25,000 to about 750,000, from about 50,000 toabout 500,000, from about 100,000 to about 400,000 grams, etc., ofethylene polymer per gram of half-metallocene titanium compound perhour, under slurry polymerization conditions, with a triisobutylaluminumco-catalyst, using isobutane as a diluent, and with a polymerizationtemperature of 80° C. and a reactor pressure of 340 psig.

Embodiment 29

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any bridged metallocene compounddisclosed herein.

Embodiment 30

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any single atom bridgedmetallocene compound with a fluorenyl group disclosed herein.

Embodiment 31

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any bridged metallocene compoundwith an alkenyl substituent disclosed herein.

Embodiment 32

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any unbridged metallocenecompound disclosed herein.

Embodiment 33

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any unbridged metallocene with acyclopentadienyl group and an indenyl group disclosed herein.

Embodiment 34

The composition defined in any one of embodiments 1-28, wherein thecatalyst composition further comprises any unbridged metallocenecompound with an alkenyl substituent disclosed herein.

Embodiment 35

The composition defined in any one of embodiments 29-34, wherein aweight ratio of the half-metallocene titanium compound to the bridgedmetallocene compound (or to the unbridged metallocene compound) in thecatalyst composition is in any range of weight ratios disclosed herein,e.g., from about 1:10 to about 10:1, from about 3:1 to about 1:3, fromabout 1.5:1 to about 1:1.5, etc.

Embodiment 36

An olefin polymerization process, the process comprising contacting thecatalyst composition defined in any one of embodiments 1-35 with anolefin monomer and an optional olefin comonomer in a polymerizationreactor system under polymerization conditions to produce an olefinpolymer.

Embodiment 37

The process defined in embodiment 36, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.Embodiment 38. The process defined in embodiment 36 or 37, wherein theolefin monomer and the optional olefin comonomer independently comprisea C₂-C₂₀ alpha-olefin.

Embodiment 39

The process defined in any one of embodiments 36-38, wherein the olefinmonomer comprises ethylene.

Embodiment 40

The process defined in any one of embodiments 36-39, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Embodiment 41

The process defined in any one of embodiments 36-40, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Embodiment 42

The process defined in any one of embodiments 36-38, wherein the olefinmonomer comprises propylene.

Embodiment 43

The process defined in any one of embodiments 36-42, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Embodiment 44

The process defined in any one of embodiments 36-43, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Embodiment 45

The process defined in any one of embodiments 36-44, wherein thepolymerization reactor system comprises a slurry reactor.

Embodiment 46

The process defined in any one of embodiments 36-45, wherein thepolymerization reactor system comprises a loop slurry reactor.

Embodiment 47

The process defined in any one of embodiments 36-46, wherein thepolymerization reactor system comprises a single reactor.

Embodiment 48

The process defined in any one of embodiments 36-46, wherein thepolymerization reactor system comprises 2 reactors.

Embodiment 49

The process defined in any one of embodiments 36-46, wherein thepolymerization reactor system comprises more than 2 reactors.

Embodiment 50

The process defined in any one of embodiments 36-49, wherein the olefinpolymer comprises any olefin polymer disclosed herein.

Embodiment 51

The process defined in any one of embodiments 36-41 and 43-50, whereinthe olefin polymer is an ethylene homopolymer, an ethylene/1-butenecopolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octenecopolymer.

Embodiment 52

The process defined in any one of embodiments 36-41 and 43-51, whereinthe olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 53

The process defined in any one of embodiments 36-38 and 42-50, whereinthe olefin polymer is a polypropylene homopolymer or a propylene-basedcopolymer.

Embodiment 54

The process defined in any one of embodiments 36-53, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Embodiment 55

The process defined in any one of embodiments 36-54, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 65° C. to about 110° C., from about 70° C. toabout 100° C., or from about 70° C. to about 95° C.

Embodiment 56

The process defined in any one of embodiments 36-55, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Embodiment 57

The process defined in any one of embodiments 36-56, wherein no hydrogenis added to the polymerization reactor system.

Embodiment 58

The process defined in any one of embodiments 36-56, wherein hydrogen isadded to the polymerization reactor system.

Embodiment 59

The process defined in embodiment 58, wherein the olefin polymer (e.g.,an ethylene/1-hexene copolymer) has an increase in melt index in anyrange disclosed herein, based on an increase in hydrogen:monomer weightratio (e.g., hydrogen:ethylene weight ratio) from 0 to 150 ppmw, e.g.,an increase of at least about 1 g/10 min (up to about 3-5 g/10 min), atleast about 1.2 g/10 min, at least about 1.5 g/10 min, at least about 2g/10 min, etc.

Embodiment 60

The process defined in any one of embodiments 36-59, wherein anorganozinc compound is added to the polymerization reactor system.

Embodiment 61

The process defined in embodiment 60, wherein the organozinc compoundcomprises diethylzinc.

Embodiment 62

The process defined in embodiment 60 or 61, wherein the addition of theorganozinc compound reduces the Mw/Mn of the olefin polymer.

Embodiment 63

The process defined in any one of embodiments 60-62, wherein theaddition of the organozinc compound reduces the z-average molecularweight (Mz) of the olefin polymer.

Embodiment 64

The process defined in any one of embodiments 36-63, wherein the olefinpolymer (e.g., an ethylene/1-hexene copolymer) has a decrease in densityin any range disclosed herein, based on an increase in comonomer:monomermolar ratio (e.g., 1-hexene:ethylene molar ratio) from 0 to 0.0176,e.g., a decrease in density of at least about 0.008 g/cm³ (up to about0.025-0.035 g/cm³), at least about 0.01 g/cm³, at least about 0.015g/cm³, at least about 0.02 g/cm³, etc.

Embodiment 65

The process defined in any one of embodiments 36-64, wherein the olefinpolymer has a ratio of Mw/Mn in any range disclosed herein, e.g., fromabout 4 to about 10, from about 4 to about 9, from about 5 to about 10,from about 4.5 to about 9.5, from about 5 to about 9, etc.

Embodiment 66

The process defined in any one of embodiments 36-65, wherein the olefinpolymer has a ratio of HLMI/MI in any range disclosed herein, e.g., fromabout 15 to about 75, from about 20 to about 70, from about 20 to about65, from about 20 to about 60, from about 25 to about 55, etc.

Embodiment 67

The process defined in any one of embodiments 36-66, wherein the olefinpolymer has a density in any range disclosed herein, e.g., from about0.89 to about 0.97, from about 0.91 to about 0.965, from about 0.91 toabout 0.94, from about 0.92 to about 0.94 g/cm³, etc.

Embodiment 68

The process defined in any one of embodiments 36-67, wherein the olefinpolymer has a conventional comonomer distribution, e.g., the number ofshort chain branches (SCB) per 1000 total carbon atoms of the polymer atMn is greater than at Mz, the number of SCB per 1000 total carbon atomsat Mn is greater than at Mw, etc.

Embodiment 69

The process defined in any one of embodiments 36-68, wherein the olefinpolymer has less than or equal to about 0.008 long chain branches (LCB)per 1000 total carbon atoms, e.g., less than or equal to about 0.005LCB, less than or equal to about 0.003 LCB, etc.

Embodiment 70

An olefin polymer produced by the polymerization process defined in anyone of embodiments 36-69.

Embodiment 71

An article comprising the olefin polymer defined in embodiment 70.

Embodiment 72

A method or forming or preparing an article of manufacture comprising anolefin polymer, the method comprising (i) performing the olefinpolymerization process defined in any one of embodiments 36-69 toproduce the olefin polymer, and (ii) forming the article of manufacturecomprising the olefin polymer, e.g., via any technique disclosed herein.

Embodiment 73

The article defined in embodiment 71 or 72, wherein the article is anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, or atoy.

We claim:
 1. An olefin polymerization process, the process comprising:contacting a catalyst composition with an olefin monomer and an optionalolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition comprises: (i) a half-metallocene titanium compound; (ii) anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion; and (iii) an optional co-catalyst; whereinthe half-metallocene titanium compound has the formula:

wherein: Cp is a cyclopentadienyl, indenyl, or fluorenyl group; each Xindependently is a monoanionic ligand; and L is a iminoimidazolidideligand; and wherein the olefin polymer has less than or equal to about0.008 long chain branches (LCB) per 1000 total carbon atoms.
 2. Theprocess of claim 1, wherein: the catalyst composition comprises anorganoaluminum co-catalyst; and the activator-support comprises afluorided solid oxide and/or a sulfated solid oxide.
 3. The process ofclaim 1, wherein the polymerization reactor system comprises a slurryreactor, gas-phase reactor, solution reactor, or a combination thereof.4. The process of claim 1, wherein the olefin monomer comprises ethyleneor propylene.
 5. The process of claim 1, wherein: the catalystcomposition comprises an organoaluminum co-catalyst comprisingtrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or any combination thereof; and theactivator-support comprises fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, or any combination thereof.
 6. Theprocess of claim 1, wherein: the catalyst composition is contacted withethylene and an olefin comonomer comprising 1-butene, 1-hexene,1-octene, or a mixture thereof; the polymerization reactor systemcomprises a loop slurry reactor; and the polymerization conditionscomprise a polymerization temperature in a range from about 65° C. toabout 110° C.
 7. The process of claim 1, wherein the olefin polymer isan ethylene polymer characterized by: a ratio of Mw/Mn in a range fromabout 4 to about 10; a ratio of HLMI/MI in a range from about 15 toabout 75; and a density in a range from about 0.90 to about 0.96 g/cm³.8. The process of claim 1, wherein the half-metallocene titaniumcompound having formula (I) has the structure of formula (III):

wherein: Cp is a cyclopentadienyl, indenyl, or fluorenyl group; each Xindependently is a monoanionic ligand; and R^(A) and R^(B) independentlyare H or a halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group.
 9. The process of claim 8, wherein, in formula(III): Cp is a substituted or unsubstituted cyclopentadienyl or indenylgroup; each X independently is a halide or C₁ to C₁₈ hydrocarbyl group;and R^(A) and R^(B) independently are H or a C₁ to C₁₈ hydrocarbylgroup.
 10. The process of claim 9, wherein: R^(A) and R^(B)independently are a C₁ to C₁₂ alkyl group; and the heterocyclic carbenegroup is unsaturated.
 11. The process of claim 1, wherein the olefinpolymer is an ethylene/α-olefin copolymer characterized by: a ratio ofMw/Mn in a range from about 5 to about 9; a ratio of HLMI/MI in a rangefrom about 25 to about 55; a density in a range from about 0.92 to about0.95 g/cm³; and less than or equal to about 0.003 long chain branches(LCB) per 1000 total carbon atoms.
 12. The process of claim 1, wherein:the olefin polymer has an increase in melt index of at least about 1g/10 min, based on an increase in hydrogen:monomer weight ratio from 0to 150 ppmw; and the olefin polymer has a decrease in density of atleast about 0.01 g/cm³, based on an increase in comonomer:monomer molarratio from 0 to 0.0176:1.
 13. The process of claim 1, wherein anorganozinc compound is added to the polymerization reactor system, andthe addition of the organozinc compound reduces the Mw/Mn of the olefinpolymer and/or reduces the z-average molecular weight (Mz) of the olefinpolymer.
 14. The process of claim 1, wherein the half-metallocenetitanium compound has any one of the following formulas:

wherein each X independently is a monoanionic ligand.
 15. The process ofclaim 14, wherein each X independently is a halide or C₁ to C₁₈hydrocarbyl group.
 16. The process of claim 14, wherein each X is Cl.17. The process of claim 1, wherein the half-metallocene titaniumcompound comprises:


18. The process of claim 1, wherein the catalyst composition furthercomprises: an unbridged zirconium based metallocene compound with acyclopentadienyl group and an indenyl group; or a bridged zirconium orhafnium based metallocene compound with a cyclopentadienyl group and afluorenyl group.
 19. An olefin polymerization process, the processcomprising: contacting a catalyst composition with an olefin monomer andan optional olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises: (i) a half-metallocene titaniumcompound; (ii) an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion; and (iii) an optional co-catalyst;wherein the half-metallocene titanium compound has the formula:

wherein: Cp is a cyclopentadienyl, indenyl, or fluorenyl group; each Xindependently is a monoanionic ligand; and L is a iminoimidazolidideligand; and wherein the olefin polymer has an increase in melt index ofat least about 1 g/10 min, based on an increase in hydrogen:monomerweight ratio from 0 to 150 ppmw.
 20. The process of claim 19, whereinthe half-metallocene titanium compound has any one of the followingformulas:

wherein each X independently is a halide or C₁ to C₁₈ hydrocarbyl group.21. The process of claim 19, wherein the activator-support comprisesfluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.
 22. The process of claim 19,wherein the olefin polymer is an ethylene polymer characterized by: aratio of Mw/Mn in a range from about 5 to about 9; a ratio of HLMI/MI ina range from about 25 to about 55; and a density in a range from about0.92 to about 0.95 g/cm³.